Stabilized yarn compositions



United States Patent 3,274,014 STABILIZED YARN COMPOSITIONS Robert C.Harrington, .Ir., and James L. Smith, Kingsport, Tenn., assignors toEastman Kodak Company,

3,274,014 Patented Sept. 20, 1966 ing compounds according to ourinvention. ferred form of titanium dioxide is rutile.

The surprising nature of our invention is confirmed by the fact that themetal alky-l phosphates, phosphites The pre- Rochester, NY a corporationof New Jersey 5 and phosp-honates used, especiallythe zinc compounds, NoDrawing. Filed Man 29 1963, sen Nm 269156 themselves show no appreciablelight absorption either 9 Claims 1. 10 177 before or after exposure tosunlight and apparently when used as yarn ultraviolet stabilizers act bysome other This application is a continuation-in-part ofHarringmechanism than that of known yarn ultraviolet staton et a1. U.S.patent application Serial No. 147,749, filed 10 bilizers, many of whichare thought to act as a reduc- October 26, 1961, and now abandoned. ingagent or absorbers for certain portions of the light This inventionrelates to man-made fibers and fabrics spectrum. Although we do not wishto be bound by made therefrom, and more particularly to such fibers andany particular theory as to why the yarn additives of fabrics resistanttoultraviolet light. our invention are effective :as ultravioletstabilizers for Man-made fibers and fabrics are susceptible todegman-made fibers and fabrics, it may be that the metal radation byultraviolet light. For example, synthetic part of the compounds exertsthe sunlight-inhibiting efpolymer yarn, as exemplified by celluloseester yarn, fect. loses both stretch and strength on exposure to light.Our invention will be further illustrated by the follow- Hence,filaments made from cellulose esters, modacrylics, ing examples. Inthese examples, yarns were spun in polyesters, poly-a-olefins,halogenated synthetic resins the conventional manner, the celluloseacetate being spun and the like would not be used in some end products,such from acetone solutions of a secondary cellulose acetate as windowcurtains or drapery linings. It therefore apcontaining about 28% acetyl,the modacrylic from a dipears desirable to render such yarn resistant toultramethyl formamide solution, and the halogenated polyviolet light.mer from an acetone solution. The cellulose ester yarns, one Object ofour invention is to Provide nad all 150 denier with 38 filaments, wereseparately woven fibers and fabrics which are resistant to ultravioletlight. as filling into a 75 denier bright acetate warp. The fabricAnother object of our invention is to provide man-made wa a 5 harnesssatin 180 ends and 70 picks per inch. filaments which are resistant toultraviolet light. Other The rough or back side of the fabrics testedwas about objects of our invention Will appearherein. 80% filling. Thisside, which was predominately the We have found that yarn compositionshaving incoryarn being tested, was exposed to light for differentporated therein a small amount of a metal monoalkyl or periods of time.After exposure, strips of the fabric were monoafyl Phosphate, metaldialkyl P p metal raveled to one inch wide strips and cut, in thedirection alkyl Phosphonate, mfillal alkyl y' P P Or of the filling,into 8 inch long strips. These strips were metal dialkyl phosphite areresistant to ultraviolet light. ulled apart i t th filling with a In tmTensile We have found Zinc, Chromium and aluminum salts to Tester. Theelongations of the strips and the pounds give best ultravioletstabilization and of these zinc to necessary to break the fabrics wererecorded and the be preferred. Preferred metal salts we have foundusepercent less in strength and elongation was calculated. ful instabilizing man-made fibers and fabrics against The test is referred toin the examples as the ravel strip deterioration from ultraviolet lightare zinc ethyl phoste t, phate, zinc diethyl phosphate, zinc dimethylphosphate, 40 EXAMPLE 1 i ethyl (ethyl phosphorlaitwizinc propylphosphite Cellulose acetate yarns containing 1.4% titanium Zmc ethylPhOSPhPHate Zmc dlpropyl Phosphate Zmc dioxide and other celluloseacetate yarns containing 1.4% lauryl phosphate, zinc stearyl phosphate,zinc butyl p titanium dioxide and 1% of various zinc salts were testedphate, chromium diethyl phosphate and aluminum ethyl by the ravel striptest after fabrics woven therefrom had P P The ethyl derivatives are tobe Preferred been exposed under glass to sunlight for different periodsespecially Zinc ethyl P P of time. The samples were inclined at a 45degree angle We have found that a small amount of titanium dioxide tothe ho i o facing outh, The results are listed in may be used inconjunction with the phosphorus-contain- Table I.

Table I Langley Units of Light Yarn Tested 30, 000 70, 000 120, 000

Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss PercentLoss in Strength in Elongation in Strength in Elongation in Strength inElongation Control, no stabilizer 12. 6 23. 4 75.0 92. 8 84. 3 94. 0Zinc monoethyl phosphate, stabilizer- 0. 5 11. 3 l6. 7 13. 2 24. 0 35. 0Zine isopropyl phosphate 2. 0 12. 8 l8. 5 15. 7 33. 5 46. 3 Zine diethylphosphate- 1. 3 10. 4 17. 7 17.8 32. 7 44. 2 Zinc ethyl phosphonate. 6.0 13. 0 l9. 5 20. 7 41. 3 55. O Zinc dipropyl phosphite. 4. 6 11. 2 l5.3 l5. 7 40. 1 39. 7 Zine ethyl (ethyl phosphonate) 5.1 10. 7 21. 2 30. 150. 3 58. 5

10,000 Langley units of light are equivalent to exposure to Floridasummer sunlight for one E onth under glass.

3 4 It may be seen from the above table that the incorpora- Table IVtion of a small amount of the salts of the invention in yarn, containinga dulling pigment, reduces the loss of Langley Units (1,000)

Percent strength and elongation caused by exposure to sunhght. sampleZinc Ethyl Percent 40 so 40 80 Phosphate TiOz Percent Loss in PercentLoss in EXAMPLE 2 Elongation Pounds Cellulose acetate filamentscontaining no dulling 'pig- Contr1o11 18 .3g S e 1... ment and celluloseacetate filaments containing 1% of amp various zinc salts of theinvention were tested in the weathepomem manner described in Example 1.The examples are shown Control 2... 0 0 s7 75 m Table II Sample 2... 1 00 78 61 Table II Langley Units of Light Yarn Tested 30, 000 70, 000 120,000

Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss PercentLoss in Strength in Elongation in Strength in Elongation in Strength inElongation Control, no stabilizer 7. 3 25. 6 40. 2 84.0 78. 3 90.0 Zincmonoethyl phosphate... 0.0 14. 7 14. 3 12. 7 19.8 30. 5 Zinc diethylphosphate 0.2 11.7 15.0 14.5 30.7 40.8 Zine ethyl phosphonate 3. o 10. 517. 6 19. 9 40. 2 50v 7 Zinc ethyl (ethyl phosphonate) 4. 3 10. 5 20. 729. 7 50. 1 57.0

The above Table II shows the reduction of the loss of EXAMPLE 5 strengthand elongation of fabrics which contain a small amount of zinc alkylphosphates and the like.

EXAMPLE 3 Various concentrations of zinc monoethyl phosphate wereincorporated in dull cellulose acetate yarn containing 1.4% TiO todetermine the efiFect of various concentrations of stabilizer 0n therate of degradation of the filaments. The samples were exposed andtested as in Example 1, and the results are lited in the followingtable.

Table III 40,000 Langley Units of Light Percent Zinc Monoethyl Phosphatein Yarn Percent Loss in Percent Loss in Strength Elongation Control, nostabilizer 15. 7 31. 2 92% 13. 5 20. 1 .5%.. 12.3 19.4 1.0%. 9.1 10. 32.0%.... 9.1 9.2

EXAMPLE 4 Zinc monoethyl phosphate and rutile titanium dioxide wereincorporated in Verel modacrylic yarn by adding to the dope from whichthe filaments were spun and the yarn evaluated for ability to resistdegradation by ex- .posure to Langley units of light and in aWeather-Ometer. The results are given in the following table.

EXAMPLE 6 An amount of zinc (ethyl phosphonate) equal to 1% based onpolymer weight was added to a 27% acetone dope of a modified vinylideneohloride-acrylonitrile copolymer (about 50:50). Yarn spun from this dopewas tested in a Fade-Ometer and showed no discoloration after hoursexposure to ultraviolet light. A control containing no additive andtested under the same conditions turned brown in 20 hours.

EXAMPLE 7 An amount of zinc bis[ethyl('ethyl phosphonate)] equal to 1%based on the polymer weight was incorporated into a 27% solids inacetone dope of a modied vinylidene chloride-acrylonitrile copolymer(about 50:50). Fibers spun from this dope were tested in a Fade-Ometerand showed no discoloration after 80 hours exposure to ultravioletlight. A control containing no additive and tested under the sameconditions turned brown in 20 hours.

EXAMPLE 8 An number of phosphate compounds were tested for their abilityto stabilize yarn against photodegradation by sunlight. Celluloseacetate was the fabric used in this instance. The results of these testsare reported in the following table.

Table V Fabric Properties Weather-Ometer Exposure 2 Original Sample No.Additive 1 600 Hrs. 1,200 Hrs.

Strength, Percent Toughness Strength, Percent Toughness Strength,Percent Toughness lbs. E 3 (S XPerlbs. E 3 Retained, lbs. E 3 Retained,

cent E Percent Percent 78526 1.0% Chromium Diethyl 22.7 23. 522.1 17.013.0 42. 3 17. 3 68 22.

Phosphate. 78527 1.0% Ziuc Lauryl Phos- 25. 0 30.0 750.0 19. 5 18. 2 47.3 16. 7 50 11.1

phate. 78528 1.0% Zinc Diethyl Phos- 23. 3 28. 3 659. 4 21.3 22. 0 71. 120. 3 19. 2 59. 0

p ate. 78529 1.0% Aluminum Ethyl 23. 4 27. 3 638. 8 19.1 18. 2 54. 415.1 6.0 14. 2

Phosphate. 78530 1.071.; Zinc Phenyl Phos- 25. 7 29. 7 763. 3 18.9 16.039. 6 16. 8 10.0 22.0

p ate. 78531 1.0%; Zine Stearyl Phos- 22. 5 23. 3 524. 2 15.9 5. 3 16. 111. 0 3.3 6. 9

p ate. 78532 1.0? Zinc Butyl Phos- 22. 4 31.0 694.4 '21. 8 21. 3 66. 917.2 10. 3 25. 5

p late. 78612 Control 26. 5 37. 3 988. 4 13. 3 4. 3 5. 8 13. 7 4. 0 5. 5

1 Added to cellulose acetate yarn containing 1.4% T103. 2 Weather-Ometerequipped with sunshine carbon are. 3 Elongation.

4 Strength.

Zinc dialkyl phosphate (2) Zinc alkyl phosphates and zinc alkyl and aryl(alkyl and aryl phosphonates) wherein the alkyl or aryl groups may bemethyl, ethyl, isopropyl, n-propyl, butyl,

lauryl or stearyl.

O O 0 Zn li R Zn O-l -O-R O I t 2 Zinc alkyl Zinc alkyl (alkylphosphonate phosphonate) (3) Zinc dialkyl phosphites where the alkylgroups include methyl, ethyl, isopropyl, n-propyl, 'butyl, lauryl orstearyl. Preferably, the alkyl group of the zinc salts is ethyl, zincmonoet-hyl phosphate being particularly useful.

When metals other than zinc are used according to our invention theabove formulas may be simply changed to substitute the Cr or Al or thelike for the Zn and modify the structure to reflect the difference invalence.

For economic reasons, We prefer to employ about .5 to 2% of the Zincsalts of the invention, based on the weight of the cellulose ester. Asomewhat wider range, say 0.1 to 5%, may generally be incorporated withgood results. Concentrations greater than 5% are detrimental to theproperties, such as toughness, of the cellulose ester.

Representative of the cellulose esters which may be stabilized accordingto our invention against deterioration caused by lengthy exposure tosunlight, especially ultraviolet rays, are the lower fatty acid estersof cellulose,

e.g., cellulose acetate and triacetate, cellulose propionate, cellulosebutyrate, cellulose acetate propionate, cellulose acetate butyrate;inorganic acid esters of cellulose such as cellulose nitrate; and,cellulose ethers such as ethyl cellulose.

We have found that it is advantageous in some instances to incorporate adulling pigment in cellulosic compositions stabilized against theeffects of ultraviolet light in accordance with our invention. Thisdulling pigment as indicated above may for example be any form oftitanium dioxide, rutile titanium dioxide being especially useful.

The invention has been described in detail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. A man-made filament yarn composed essentially of a fiber-formingcomposition selected from the group consisting of cellulose esters,acrylonitrile copolymers, polyesters and poly-alpha-olefins stabilizedagainst deterioration from ultraviolet light containing 0.1 to 5%, basedon the weight of the yarn, of a salt selected from the group consistingof (1) metal salts of monoalkyl, monoaryl and dialkyl acid phosphates;2) metal alkyl phosphonates and metal alkyl (alkyl phosphonates), and(3) metal dialkyl phosphites, said alkyl and aryl groups containing from1 to 18 carbon atoms and said metal being selected from the groupconsisting of zinc, chromium and aluminum.

2. In the method of preparing cellulose acetate yarns wherein celluloseacetate is dissolved in a solvent and filaments are extruded therefrom,the step which comprises adding to the solution of cellulose acetate andsolvent 0.5 to 2%, based on the weight of the cellulose acetate, of acompound selected from the group consisting of a metal monoalkylphosphate, a metal monoaryl phosphate, a metal dialkyl phosphate, ametal alkyl phosphonate, a metal alkyl (alkyl phosphonate) and a metaldialkyl phosphite, said alkyl and aryl groups containing 1-18 carbonatoms, said metal being selected from the group consisting of zinc,chromium and aluminum, and a delustering amount of titanium dioxide.

3. Cellulose ester compositions containing .1 to 5%, base on the weightof the cellulose ester, of a compound selected from the group consitingof (1) metal salts of monoalkyl, monoa ryl and dialkyl acid phosphates,(2)

metal alkyl phosphonates and metal alkyl (alkyl phosphonates), and (3)metal dialkyl phosphites, said alkyl and aryl groups containing from 1to 18 carbon atoms and said metal being selected from the groupconsisting of zinc, chromium and aluminum.

4. Cellulose ester compositions containing .1 to 5%;

based on the weight of the cellulose ester, of zinc monoethyl phosphateand a delustering amount of titanium dioxide.

5. Cellulose acetate compositions containing .1 to 5%, based on theweight of the cellulose acetate, of zinc monoethyl phosphate.

6. A man-made filament fabric of a yarn composed essentially of .afiber-forming composition selected from the group consisting ofcellulose esters, acrylonitrile copolymers, polyesters andpoly-alpha-olefins stabilized against deterioration from ultravioletlight containing 0.1-5%, based on the weight of the yarn in said fabric,of a salt selected from the group consisting of (1) metal salts ofmonoalkyl, monoaryl and dialkyl acid phosphates, (2) metal alkylphosphonates and metal alkyl (alkyl phosphonates), and (3) metal dialkylphosphites, said alkyl and aryl groups containing from 1-18 carbon atomsand said metal being selected from the group consisting of zinc,chromium and aluminum.

7. A man-made filament fabric as defined by claim 6 wherein the fiberforming composition is" a cellulosic ester.

" "S.' A man-made filament fabric as defined by claim 6 wherein saidsalt is zinc monoethyl phosphate.

9. A man-made filament fabric as defined by claim 6 wherein the fiberforming composition contains from 0.1 to 5%, based on the Weight of thefabric, of rutile titanium dioxide.

References Cited by the Examiner ALEXANDER H. BRODMERKEL, PrimaryExaminer.

L. B. HAYES, Assistant Examiner.

1. A MAN-MADE FILAMENT YARN COMPOSED ESSENTIALLY OF A FIBER-FORMINGCOMPOSITION SELECTED FROM THE GROUP CONSISTING OF CELLULOSE ESTERS,ACRYLONITRILE COPOLYMERS, POLYESTERS AND POLY-ALPHA-OLEFINS STABILIZEDAGAINST DETERIORATION FROM ULTRAVIOLET LIGHT CONTAINING 0.1 TO 5%, BASEDON THE WEIGHT OF YARN, OF A SALT SELECTED FROM THE GROUP CONSISTING OF(1) METAL SALTS OF MONOALKYL, MONOARYL AND DIALKYL ACID PHOSPHATES; (2)METAL ALKYL PHOSPHONATES AND METAL ALKYL (ALKYL PHOSPHONATES), AND (3)METAL DIALKYL PHOSPHITES, SAID ALKYL AND ARYL GROUPS CONTAINING FROM 1TO 8 CARBON ATOMS AND SAID METAL BEING SELECTED FROM THE GROUPCONSISTING OF ZINC, CHROMIUM AND ALUMIMUM.